EP0222098A2 - Water soluble triphenodioxazine compounds, process for their preparation and their use as dyestuffs - Google Patents

Abstract

Tripbendioxazin compounds with fiber-reactive dye properties corresponding to the general formula (1) <IMAGE> in which T is an optionally substituted alkyl group of 1 to 6 carbon atoms, with the exception of a radical of the group Y defined below, the alkyl group still being interrupted by heteroatoms can, or is an optionally substituted aryl group, B is an oxygen or sulfur atom or an amino group, W is a bivalent, optionally substituted aliphatic, cycloaliphatic, araliphatic or aromatic-carbocyclic radical or a benzotriazole radical combined with one of these radicals, the aliphatic radicals being represented by Hetero groups can be interrupted and or aliphatic and aryl radicals can be connected to one another by a hetero group, R is hydrogen, alkyl of 1 to 6 C atoms, alkoxy of 1 to 5 C atoms, halogen, carboxy or sulfo, X 1 is hydrogen, halogen, Cycloalkyl, aralkyloxy, alkoxy, aryloxy, alkyl, Aryl, aralkyl, cyan, carboxy, carbalkoxy, arylamino, carbamoyl, optionally substituted, alkanoylamino or aroylamino and X² can have the meaning of X¹, n represents the number 1 or 2, Y is the vinyl group or one in the β-position by one alkaline eliminable substituent is substituted ethyl group and the molecule 81) contains at least one sulfo or sulfato group.

Description

The present invention is in the field of fiber reactive dyes.

From European patent application publication No. 0 141 996 A, symmetrically constructed fiber-reactive triphendioxazine dyes are already known, but they still have properties that can be improved.

gefunden, die wertvolle faserreaktive Farbstoffeigenschaften besitzen.New water-soluble triphendioxazine compounds corresponding to the general formula (1) have now been

found that have valuable fiber-reactive dye properties.

• T ist eine gegebenenfalls substituierte Alkylgruppe (einschließlich Aralkyl) von 1 bis 6 C-Atomen, bevorzugt von 1 bis 4 C-Atomen, ausgenommen ein Rest der nachstehend definierten Gruppe Y, wobei die Alkylgruppe noch durch Heterogruppen, bevorzugt 1 oder 2 Heterogruppen, die aus Gruppen der Formeln -0- , -S- , -NH- und -N(R')-mit R' der nachstehend angegebenen Bedeutung ausgewählt sind, unterbrochen sein kann, oder ist eine gegebenenfalls substituierte Arylgruppe;
• B ist ein Sauerstoff- oder Schwefelatom oder eine Aminogruppe der Formel -NH- oder -N(R')- ,
  in welcher
  • R' eine Alkylgruppe von 1 bis 6 C-Atomen, bevorzugt von 1 bis 4 C-Atomen, wie insbesondere die Methyl- oder Ethylgruppe, ist, die substituiert sein kann;
• W ist ein bivalenter, gegebenenfalls substituierter aliphatischer, gegebenenfalls durch Alkyl substituierter (C₅-C₁₀)-cycloaliphatischer, gegebenenfalls durch Alkyl substituierter aliphatisch-(C₅-C₈)-cycloaliphatischer, gegebenenfalls substituierter araliphatisiher oder gegebenenfalls substituierter aromatisch-carbocyclischer Rest oder ein mit einem dieser Reste kombinierter Benzotriazolrest, wobei die aliphatischen Reste in W durch Heterogruppen, bevorzugt 1 oder 2 Heterogruppen, unterbrochen sein können, die aus den Gruppen -O- , -S- , -SO₂- , -CO- , 1,4-Piperidino, -NH- und -N(R^o)-worin R^O eine der Bedeutungen von R' hat oder eine Alkanoylgruppe von 2 bis 5 C-Atomen, wie Acetylgruppe, ist, ausgewählt sind, und/oder wobei aliphatische und Arylreste durch eine solche Heterogruppe miteinander verbunden sein können;
• W hat eine für W angegebene Bedeutung und ist mit W gleich oder von W verschieden;
• R ist ein Wasserstoffatom oder ein Alkyl von 1 bis 6 C-Atomen, bevorzugt von 1 bis 4 C-Atomen, wie insbesondere hiervon Methyl und Ethyl, ein Alkoxy von 1 bis 5 C-Atomen, bevorzugt von 1 bis 4 C-Atomen, wie insbesondere hiervon Methoxy und Ethoxy, ein Halogen, wie Fluor und Brom und insbesondere Chlor, Carboxy oder Sulfo;
• X¹ ist ein Wasserstoffatom oder ein Halogenatom, wie Fluor und insbesondere ein Chlor- oder Bromatom, eine Cycloalkylgruppe von 5 bis 8 C-Atomen, wie die Cyclohexylgruppe, eine Aralkyloxygruppe, eine Alkoxygruppe von 1 bis 4 C-Atomen, wie die Methoxygruppe, eine Aryloxygruppe, eine Alkylgruppe von 1 bis 4 C-Atomen, wie die Methylgruppe, eine Arylgruppe, eine Aralkylgruppe, eine Cyangruppe, eine Carboxygruppe, eine Carbalkoxygruppe von 2 bis 5 C-Atomen, wie die Carbomethoxy- oder Carbethoxygruppe, eine Arylaminogruppe, eine Carbamoyl- gruppe, eine N-Alkyl-carbamoyl-Gruppe oder N,N-Dialkyl- carbamoyl-Gruppe mit Alkylresten von jeweils 1 bis 4 C-Atomen, eine N-Aryl-carbamoyl-Gruppe, eine Alkanoylaminogruppe von 2 bis 5 C-Atomen, wie die Acetylaminogruppe, oder eine Aroylaminogruppe, wie die Benzoylaminogruppe, wobei die Arylreste in diesen genannten Substituenten bevorzugt Phenylreste sind, die noch durch 1 oder 2 Substituenten aus der Gruppe Halogen, wie Chlor, Nitro, Alkyl von 1 bis 4 C-Atomen, Alkoxy von 1 bis 4 C-Atomen, Carboxy und Sulfo substituiert sein können und wobei X¹ bevorzugt ein Wasserstoffatom, eine Alkanoylaminogruppe von 2 bis 5 C-Atomen, eine Phenoxygruppe, die substituiert sein kann, eine Alkoxygruppe von 1 bis 4 C-Atomen, eine Alkylgruppe von 1 bis 4 C-Atomen und insbesondere bevorzugt ein Chloratom oder Bromatom ist;
• _X ² ist mit X gleich oder von X¹ verschieden und hat eine der für X angegebenen Bedeutungen;
• die Gruppe -S0₂-T steht bevorzugt in ortho-Stellung zur Gruppe -B-W-(S0₂-Y)_n bzw. -B-W¹-(SO₂-Y)_n gebunden;
• n ist die Zahl 1 oder 2, bevorzugt jedoch 1;
• Y ist die Vinylgruppe oder eine Ethylgruppe, die in β-Stellung einen durch ein Alkali eliminierbaren Substituenten enthält;
• von den Sulfo- und Sulfatogruppen, die im Molekül (1) enthalten sein können, enthält das Molekül (1) zwingend mindestens eine, bevorzugt mindestens zwei davon.

In this formula (1):

• T is an optionally substituted alkyl group (including aralkyl) of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, with the exception of a radical of the group Y defined below, where the alkyl group is also replaced by hetero groups, preferably 1 or 2 hetero groups can be interrupted from groups of the formulas -0-, -S-, -NH- and -N (R ') - where R' has the meaning given below, or is an optionally substituted aryl group;
• B is an oxygen or sulfur atom or an amino group of the formula -NH- or -N (R ') -,
  in which
  • R 'is an alkyl group of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, such as in particular the methyl or Is ethyl group, which may be substituted;
• W is a bivalent, optionally substituted aliphatic, optionally substituted by alkyl (C ₅ -C ₁₀ ) -cycloaliphatic, optionally substituted by alkyl aliphatic- (C ₅ -C ₈ ) -cycloaliphatic, optionally substituted araliphatic or optionally substituted aromatic-carbocyclic radical or a benzotriazole residue combined with one of these residues, it being possible for the aliphatic residues in W to be interrupted by hetero groups, preferably 1 or 2 hetero groups, which consist of the groups -O-, -S-, -SO ₂ -, -CO-, 1, 4-Piperidino, -NH- and -N (R ^o ) -worin R ^{O has} one of the meanings of R 'or an alkanoyl group of 2 to 5 carbon atoms, such as acetyl group, is selected, and / or wherein aliphatic and Aryl radicals can be connected to one another by such a hetero group;
• W has a meaning given for W and is the same as or different from W;
• R is a hydrogen atom or an alkyl of 1 to 6 carbon atoms, preferably of 1 to 4 carbon atoms, such as especially methyl and ethyl, an alkoxy of 1 to 5 carbon atoms, preferably of 1 to 4 carbon atoms, such as in particular methoxy and ethoxy, a halogen such as fluorine and bromine and in particular chlorine, carboxy or sulfo;
• X ¹ is a hydrogen atom or a halogen atom, such as fluorine and in particular a chlorine or bromine atom, a cycloalkyl group of 5 to 8 C atoms, such as the cyclohexyl group, an aralkyloxy group, an alkoxy group of 1 to 4 C atoms, such as the methoxy group, an aryloxy group, an alkyl group of 1 to 4 carbon atoms, such as the methyl group, an aryl group, an aralkyl group, a cyano group, a carboxy group, a carbalkoxy group of 2 to 5 carbon atoms, such as the carbomethoxy or carbethoxy group, an arylamino group, a Carbamoyl group, an N-alkyl-carbamoyl group or N, N-dialkyl-carbamoyl group with alkyl radicals of 1 to 4 carbon atoms each, an N-aryl-carbamoyl group, an alkanoylamino group of 2 to 5 carbon atoms Atoms, such as acetylamino group, or an aroylamino group, such as the benzoylamino group, where the aryl radicals in these substituents mentioned are preferably phenyl radicals which are also substituted by 1 or 2 substituents from the group halogen, such as chlorine, nitro, alkyl of 1 to 4 carbon atoms, alkoxy of 1 up to 4 carbon atoms, carboxy and sulfo can be substituted and wherein X ¹ preferably represents a hydrogen atom, an alkanoylamino group of 2 to 5 carbon atoms, a phenoxy group which can be substituted, an alkoxy group of 1 to 4 carbon atoms, an alkyl group from 1 to 4 carbon atoms and particularly preferably a chlorine atom or bromine atom;
• _X ² is identical to or different from X ¹ and has one of the meanings given for X;
• the group -S0 ₂ -T is preferably bound in the ortho position to the group -BW- (S0 ₂ -Y) _n or -BW ¹ - (SO ₂ -Y) _n ;
• n is the number 1 or 2, but preferably 1;
• Y is the vinyl group or an ethyl group which contains an alkali-eliminable substituent in the β-position;
• Of the sulfo and sulfato groups which can be contained in the molecule (1), the molecule (1) contains at least one, preferably at least two, of them.

The individual formula elements, which also appear twice, can have meanings which are the same or different from one another.

in entsprechender Weise ein für W erwähnter, mit einem der aliphatischen oder aromatischen Reste kombinierter Benzotriazolrest beispielsweise ein Rest der allgemeinen Formel (2B)

in welchen W^* und W^x jeweils einen bivalenten, gegebenenfalls substituierten aliphatischen, gegebenenfalls durch Alkyl substituierten (C₅-C₁₀)-cycloaliphatischen, gegebenenfalls durch Alkyl substituierten aliphatisch-(C₅-C_a)-cycloaliphatischen, gegebenenfalls substituierten araliphatischen oder gegebenenfalls substituierten aromatisch-carbocyclischen Rest bedeuten, wobei die aliphatischen Reste in _W* bzw. _W ^x durch Heterogruppen, bevorzugt 1 oder 2 Heterogruppen, die aus den Gruppen der Formeln -O- , -S- , -S0₂- , -CO- , 1,4-Piperidino, -NH- und -N(R°)- mit R^O der obengenannten Bedeutung ausgewählt sind, unterbrochen sein können und/oder aliphatische und Arylreste durch eine solche Heterogruppe miteinander verbunden sein können, und in welchen R^* jeweils ein Wasserstoffatom, eine Alkylgruppe von 1 bis 4 C-Atomen, wie die Methyl- oder Ethyl- gruppe, eine Alkoxygruppe von 1 bis 4 C-Atomen, wie die Methoxy- oder Ethoxygruppe, ein Halogenatom, wie Chloratom, oder eine Carboxy- oder Sulfogruppe bedeutet.A benzotriazole radical mentioned for W ¹ and combined with an aliphatic or aromatic radical is, for example, a radical of the general formula (2A)

in a corresponding manner, a benzo mentioned for W, combined with one of the aliphatic or aromatic radicals triazole radical, for example a radical of the general formula (2B)

in which W ^* and W ^x each have a bivalent, optionally substituted aliphatic, optionally substituted by alkyl (C ₅ -C ₁₀ ) cycloaliphatic, optionally substituted by alkyl aliphatic (C ₅ -C _a ) cycloaliphatic, optionally substituted araliphatic or optionally substituted aromatic-carbocyclic radical, where the aliphatic radicals in _W * or _W ^x by hetero groups, preferably 1 or 2 hetero groups, which consist of the groups of the formulas -O-, -S-, -S0 ₂ -, -CO-, 1,4-piperidino, -NH- and -N (R °) - are selected with R ^{O of} the abovementioned meaning, can be interrupted and / or aliphatic and aryl radicals can be connected to one another by such a hetero group, and in which R ^{* in} each case a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, such as the methyl or ethyl group, an alkoxy group of 1 to 4 carbon atoms, such as the methoxy or ethoxy group, a halogen atom, such as chlorine atom, or a carbox y or sulfo group means.

Aryl radicals in the groups mentioned above or below are in particular the phenyl and naphthyl radicals; they can be substituted, for example by substituents from the group alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, halogen, such as chlorine and bromine, sulfo, carboxy , Sulfamoyl, carbamoyl, by phenyl, alkyl of 1 to 4 carbon atoms, phenylalkyl with an alkyl radical of 1 to 4 carbon atoms and / or cycloalkyl of 5 to 8 carbon atoms mono- or disubstituted carbamoyl, by phenyl, alkyl of 1 to 4 carbon atoms, phenylalkyl with an alkyl radical of 1 to 4 carbon atoms and / or cycloalkyl of 5 to 8 carbon atoms mono- or disubstituted sulfamoyl, trifluoromethyl, benzoylamino, sulfobenzoylamino, alkanoylamino of 2 to 5 carbon atoms, nitro, amino and optionally mono- or disubstituted amino, where the substituents of optionally substituted aliphatic (including araliphatic), optionally substituted aryl and _(C5-C8) cycloalkyl are moieties.

Aryl radicals in the araliphatic radicals are in particular phenylene and naphthylene radicals; they can be substituted, for example by substituents from the group alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms, such as methoxy and ethoxy, halogen, such as chlorine and bromine, sulfo, carboxy , Sulfamoyl, carbamoyl, mono- or disubstituted carbamoyl by phenyl, alkyl of 1 to 4 carbon atoms, phenylalkyl with an alkyl radical of 1 to 4 carbon atoms and / or cycloalkyl of 5 to 8 carbon atoms, by phenyl, alkyl of 1 to 4 carbon atoms, phenylalkyl with an alkyl radical of 1 to 4 carbon atoms and / or cycloalkyl of 5 to 8 carbon atoms, mono- or disubstituted sulfamoyl, trifluoromethyl, benzoylamino, sulfobenzoylamino, alkanoylamino of 2 to 5 carbon atoms, Nitro, amino and optionally mono- or disubstituted amino, the substituents of which are optionally substituted aliphatic (including araliphatic), optionally substituted aryl and (C ₅ -C _S ) cycloalkyl radicals.

Aromatic-carbocyclic radicals are, for example, phenylene and naphthylene or phenyl and naphthyl radicals which can be substituted, for example by substituents from the group of alkyl of 1 to 4 carbon atoms, such as methyl and ethyl, alkoxy of 1 to 4 carbon atoms -Atoms, such as methoxy and ethoxy, halogen, such as chlorine and bromine, sulfo, carboxy, sulfamoyl, carbamoyl, by phenyl, alkyl of 1 to 4 carbon atoms, phenylalkyl with an alkyl radical of 1 to 4 carbon atoms and / or cycloalkyl of 5 to 8 carbon atoms mono- or disubstituted carbamoyl, by phenyl, alkyl of 1 to 4 carbon atoms, phenylalkyl with an alkyl radical of 1 to 4 carbon atoms and / or cycloalkyl of 5 to 8 carbon atoms Atoms mono- or disubstituted sulfamoyl, trifluoromethyl, benzoylamino, sulfobenzoylamino, alkanoylamino of 2 to 5 carbon atoms, nitro, amino and optionally mono- or disubstituted amino, the substituents of which are optionally substituted aliphatic (including araliphatic), optionally substituted aryl and ( C ₅ -C ₈ cycloalkyl radicals, of which particular preference is given to those phenylene or phenyl radicals which are substituted by substituents from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms and sulfo and / or by optionally mono- or disubstituted amino group can be substituted.

Aliphatic radicals are, for example, alkyl groups or alkylene groups each having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, which can be substituted. Substituted alkyl and alkylene groups are, for example, those which are substituted by 1 or 2 substituents from the group chlorine, alkoxy of 1 to 4 carbon atoms, benzoylamino, sulfobenzoylamino, alkanoylamino of 2 to 5 carbon atoms, hydroxyl, sulfato, phosphato, acetyloxy, Sulfo, carboxy or optionally substituted aryl may be substituted. Preferred substituents hereof are the carboxy and sulfo groups and sulfato groups.

The formula members W and W and W ^* and W ^x are, for example, alkylene groups of 1 to 6 carbon atoms, in particular of 2 to 4 carbon atoms, the alkylene chain being composed of 1 or 2 hetero groups, preferably from the groups -O-, -NH- and -N (R ') - are selected with R' of the above meaning, may be interrupted, or an alkylene-phenylene, a phenylene-alkylene, a phenylene-alkylene-phenylene or alkylene-phenylene-alkylene Radical, wherein in these araliphatic radicals the alkylene radicals are those of 1 to 6, preferably 1 to 4, carbon atoms and, if appropriate, by those specified be substituted and / or interrupted by one or two of the hetero groups mentioned and the benzene nuclei can each be substituted by 1 or 2 substituents selected from the group of the substituents of sulfo, carboxy, sulfamoyl, carbamoyl, methyl, ethyl, methoxy , Ethoxy, nitro, chlorine, amino and amino substituted by optionally substituted aliphatic and / or optionally substituted aryl radicals, where in the event that an alkylene group is interrupted by hetero groups, the alkylene portions of which are preferably those of 2 or 3 carbon atoms, and wherein the aliphatic and aryl radicals can still be connected by an oxygen atom or a group -NH-. The _F ormelglieder W and W ¹ and W ^* and W ^x are furthermore, for example, a phenylene radical, in particular a meta- or para-phenylene or by 1 or 2 substituents from the group comprising sulfo, carboxy, sulfamoyl, carbamoyl, methyl, ethyl , Methoxy, ethoxy, chlorine, amino and amino substituted by optionally substituted aliphatic and / or optionally substituted aryl radicals, but preferably by sulfo, or a naphthylene radical optionally substituted by sulfo.

W or W, W ^* and W is preferably an alkylene radical of 2 to 4 carbon atoms which can be substituted by 1 or 2 substituents, preferably one substituent from the group sulfo, sulfato, carboxy, phenyl and sulfophenyl, or W or W is a phenylene radical which can be substituted by 1 or 2 substituents, preferably one substituent, from the group sulfo, carboxy, methyl, methoxy, ethoxy and chlorine, or W or W, W ^* and W are preferably an alkylenephenylene -Rest from these residues, which may also be connected by an oxygen atom or a group -NH-.

The fiber-reactive groups of the formula -S0 ₂ -Y are bonded to aliphatic and / or aromatic C atoms, preferably aromatic C atoms, of W or W ¹ .

in welchen M eine der später angegebenen Bedeutungen besitzt und R^ß für Wasserstoff oder Sulfo steht.W ^* radicals are, for example, the meta or para-phenylene radical, the 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 2 -Methyl-l, 3-propylene, 2-sulfophenyl-1,3-propylene and 2-sulfato-1,3-propylene radical, furthermore, for example, a sulfo-substituted 1,4-phenylene radical, a 1,4- and 1 , 3-cyclohexylene radical, a divalent radical of the formulas (a ^* ) to (z ^* ) given below, preferably the 1,2-ethylene, 1,3-propylene and 1,4-butylene radical, the rest of the Formulas (a ^* ), a 2-sulfophenyl-1,3-propylene and a 2-sulfato-1,3-propylene radical and a sulfo-substituted 1,4-phenylene radical:

in which M has one of the meanings given later and R ^{ß is} hydrogen or sulfo.

The residues W ^x are, for example, the groups just mentioned for W ^* , but arranged in a “mirror image”.

worin M eine der später angegebenen Bedeutungen besitzt, _R ² eine ß-Sulfatoethyl-Gruppe ist, R³ Wasserstoff ist oder Alkyl von 1 bis 4 C-Atomen, das substituiert sein kann, wie beispielsweise durch Sulfo, Carboxy, Sulfato, Phenyl oder Sulfophenyl, bevorzugt Sulfo oder Carboxy, und R⁴ ein Alkyl von 1 bis 4 C-Atomen bedeutet, das substituiert sein kann, wie durch Sulfo, Carboxy, Sulfato, Phenyl und Sulfophenyl, bevorzugt Sulfo oder Carboxy, oder ein gegebenenfalls substituiertes, wie durch Sulfo oder Carboxy substituiertes, Phenyl ist, wobei beispielsweise die Aminogruppe der allgemeinen Formel -NR³R⁴ eine Ethylamino-, Diethylamino-, β-Sulfatoethylamino-, β-Sulfoethylamino-, N-Methyl-N-ß-sulfoethylamino- oder N-Methyl-N-ß-sulfatoethylamino-Gruppe ist.W ¹ radicals are, for example, the meta- or para-phenylene radical, the 1,2-ethylene and 1,3-propylene radical or a divalent radical of the formulas (a) to ( _z ) given below, where W ^{1 is} preferably a radical of the formula (b), (g), (m), (q), (x), (y) or (z) is:

wherein M has one of the meanings given later, _R ^{2 is} a β-sulfatoethyl group, R ^{3 is} hydrogen or alkyl of 1 to 4 carbon atoms, which may be substituted, such as by sulfo, carboxy, sulfato, phenyl or sulfophenyl , preferably sulfo or carboxy, and R ^{4 is} an alkyl of 1 to 4 carbon atoms which can be substituted, such as by sulfo, carboxy, sulfato, phenyl and sulfophenyl, preferably sulfo or carboxy, or an optionally substituted, such as by sulfo or carboxy-substituted phenyl, where, for example, the amino group of the general formula -NR ³ R ^{4 is} ethylamino, diethylamino, β-sulfatoethylamino, β-sulfoethylamino, N-methyl-N-ß-sulfoethylamino or N-methyl -N-β-sulfatoethylamino group.

The radicals W are, for example, the groups just mentioned for W ¹ , but arranged in a “mirror image”.

The formula radical T is preferably an alkyl radical of 2 to 6, particularly preferably of 2 or 3 carbon atoms, which is substituted by a sulfo or carboxy group.

Substituents which are bonded according to the formula Y in the β-position of the ethyl group and can be eliminated by an alkali to form the vinyl group are, for example, alkanoyloxy groups of 2 to 5 carbon atoms, such as the acetyloxy group, aroyloxy groups, such as the benzoyloxy, sulfobenzoyloxy - Or carboxybenzoyloxy group, dialkylamino groups with alkyl radicals from 1 to 4 carbon atoms, such as especially the dimethylamino and diethylamino group, trialkylammonium groups with alkyl radicals from 1 to 4 carbon atoms, such as the trimethylammonium group, the chlorine atom, the bromine atom, alkylsulfonyloxy groups with alkyl radicals 1 to 4 carbon atoms, a phosphato group, a thiosulfato group or a sulfato group. Of the groups corresponding to the formula member Y, preference is given to the B-chloroethyl, β-phosphatoethyl, β-acetyloxyethyl and β-thiosulfatoethyl group and in particular the vinyl group and very particularly preferably the β-sulfatoethyl group.

The two formula radicals Y in the general formula (1) can have mutually identical or different meanings; they preferably have the same meaning. Likewise, the formula radicals (Y-SO ₂ ) _n -WB- and -BW ¹ - (SO ₂ -Y) _{n may} have meanings which are identical to or different from one another; they preferably have the same meaning. Likewise, the formula radicals -S0 ₂ -T can have the same or different meanings to one another; they preferably have the same meaning.

• M ist ein Wasserstoffatom oder ein Alkalimetall, wie Natrium, Kalium und Lithium, oder das Äquivalent eines Erdalkalimetalls, wie beispielsweise des Calciums, insbesondere jedoch ein Alkalimetall.

Sulfo groups are groups corresponding to the general formula -SO ₃ M, carboxy groups are groups corresponding to the general formula -COOM, sulfato groups are groups corresponding to the general formula -OSO ₃ M, thiosulfato groups are groups corresponding to the general formula -S-SO ₃ M and phosphato groups Groups corresponding to the general formula -OPO ₃ M ₂ , where M, as later, has the following meaning:

• M is a hydrogen atom or an alkali metal such as sodium, potassium and lithium, or the equivalent of an alkaline earth metal such as calcium, but especially an alkali metal.

In the general formula (1) R is preferably a hydrogen atom, furthermore B preferably an amino group -NH-, furthermore the radical W preferably a radical of the above formula (b), (m), (y) or (z) and W preferred a corresponding remainder with a "mirror image" structure; the formula radical T is furthermore preferably a B-sulfoethyl group.

entsprechen, in welcher

• X für ein Bromatom oder bevorzugt ein Chloratom steht,
• M ein Wasserstoffatom oder bevorzugt ein Alkalimetallatom, wie insbesondere Natrium, ist,
• p für die Zahl 2 oder 3, bevorzugt 2, steht,
• _R" eine Sulfo-, Sulfato- oder Carboxy, bevorzugt Sulfogruppe bedeutet, im Falle von p = 2 jedoch keine Sulfatogruppe bedeutet,
• _W ¹ einen Phenylenrest, bevorzugt meta-Phenylenrest, darstellt, der durch Methyl, Ethyl, Chlor, Methoxy oder Ethoxy substituiert sein kann, bevorzugt durch eine Methoxygruppe substituiert ist, wie ein Rest der Formel (m), oder eine Gruppe der Formel (2a), (2b) oder (2c)
  
  
  oder der obigen Formel (g) oder (q)
  mit M der obengenannten Bedeutung ist, wobei in den Formeln (2b) und (2c) der Phenylenrest bevorzugt ein meta-Phenylenrest ist und die Aminogruppe in para-Stellung zur anderen, dem Formelrest B entsprechenden Aminogruppe gebunden ist, und
• W einen solchen für W erwähnten, jedoch "spiegelbildlich" angeordneten Rest bedeutet.

Of particular note of the triphendioxazine compounds according to the invention are those which have the general formula (Ia)

correspond in which

• X represents a bromine atom or preferably a chlorine atom,
• M is a hydrogen atom or preferably an alkali metal atom, such as in particular sodium,
• p represents the number 2 or 3, preferably 2,
• _R "denotes a sulfo, sulfato or carboxy, preferably sulfo group, but in the case of p = 2 means no sulfato group,
• _W ^{1 represents} a phenylene radical, preferably meta-phenylene radical, which can be substituted by methyl, ethyl, chlorine, methoxy or ethoxy, preferably substituted by a methoxy group, such as a radical of the formula (m), or a group of the formula (2a ), (2b) or (2c)
  
  
  or the above formula (g) or (q)
  where M is the meaning given above, where in the formulas (2b) and (2c) the phenylene radical is preferably a meta-phenylene radical and the amino group is in the para position is bound to the other amino group corresponding to the formula radical B, and
• W means such a remainder as mentioned for W, but arranged "mirror image".

The new dioxazine compounds can be present both in acid form and in the form of their salts. They are preferably in the form of the salts, in particular the alkali metal salts, and are also preferably used in the form of these salts for dyeing (here and hereinafter in the general sense and including printing), of materials containing hydroxyl and / or carbonamide groups, in particular fiber materials.

(in welcher Y' die Vinylgruppe, die β-Hydroxy-ethyl-Gruppe oder eine Ethylgruppe, die in β-Stellung einen durch ein Alkali eliminierbaren Substituenten, wie einen der für Y genannten, enthält, bevorzugt die β-Hydroxyethyl-Gruppe ist, und n, R, B, W, W¹, T, X¹ und X² die obengenannten Bedeutungen haben, wobei substituierte Alkylgruppen in diesen Resten auch hydroxysubstituierte Alkylgruppen sein können und die Gruppen -S0₂-T bevorzugt in ortho-Stellung zur Gruppe (Y'-SO₂)_n-W-B- bzw. -B-W¹-(SO₂-Y')_n gebunden sind) in saurem Medium und vorzugsweise in Gegenwart eines Oxidationsmittels zum Triphendioxazin cyclisiert. Die Umsetzung erfolgt in an und für sich bekannter Verfahrensweise, so beispielsweise in Schwefelsäure oder Schwefeltrioxid enthaltender Schwefelsäure als Reaktionsmedium, wobei als Oxidationsmittel Schwefeltrioxid, Ammonium- oder Alkalipersulfate, Jod oder anorganische Jodverbindungen in Gegenwart von Oleum, Natriumborat, vorzugsweise jedoch Natrium- oder Kaliumperoxodisulfat (entsprechend den Formeln Na₂S₂O₈ bzw. K₂S₂O₈), verwendet werden. Solche Verfahrensweisen sind bspw. aus der britischen Patentschrift Nr. 1 589 915 und der europäischen Patentanmeldungs-Veröffentlichung Nr. 0 141 359A bekannt.The present invention further relates to processes for the preparation of the abovementioned and defined compounds of the general formula (1). These are characterized in that a compound of the general formula (3)

(in which Y 'is the vinyl group, the β-hydroxyethyl group or an ethyl group which, in the β position, contains a substituent which can be eliminated by an alkali, such as one mentioned for Y, preferably the β-hydroxyethyl group, and n, R, B, W, W ¹ , T, X ¹ and X ^{2 have} the meanings given above, where substituted alkyl groups in these radicals can also be hydroxy-substituted alkyl groups and the groups -S0 ₂ -T preferably in the ortho position to the group (Y'-SO ₂ ) _n -WB- or -BW ¹ - (SO ₂ -Y ') _{n are} bound) in an acidic medium and preferably in the presence of a Oxidizing agent cyclized to triphendioxazine. The reaction is carried out in a manner known per se, for example in sulfuric acid containing sulfuric acid or sulfur trioxide as the reaction medium, using sulfur trioxide, ammonium or alkali persulfates, iodine or inorganic iodine compounds in the presence of oleum, sodium borate, but preferably sodium or potassium peroxodisulfate ( according to the formulas Na ₂ S ₂ O ₈ or K ₂ S ₂ O ₈ ) can be used. Such procedures are known, for example, from British Patent No. 1,589,915 and European Patent Application Publication No. 0 141 359A.

The reaction is preferably carried out in concentrated sulfuric acid, such as 96% to preferably 100% sulfuric acid, and in particular in sulfuric acid (oleum) containing sulfur trioxide, such as up to 50% by weight oleum. The reaction temperature is chosen between 0 and 80 ° C. The oleum used as the reaction medium and agent generally has a content of 5 to 30% by weight, preferably 10 to 20% by weight, of sulfur trioxide. If peroxodisulfate is added as the oxidizing agent, the cyclization is carried out between 0 and 40 ° C, preferably between 15 and 25 ° C. When using oleum / peroxodisulfate, the reaction temperature should not exceed 30 ° C. 10 to 20% oleum is preferred using an amount of peroxodisulfate equivalent to compound (3). With iodine as the oxidizing agent, this is used in catalytic amounts in 10 to 50% oleum; here the reaction temperature is usually between 0 and 40 ° C.

Optionally before or simultaneously with the cyclization or only after the cyclization reaction, any hydroxyalkyl groups, such as, for example, may be present the B-hydroxyethyl group of the formula radical Y ', by means of a sulfating or phosphating agent, such as 96-100% sulfuric acid or sulfuric acid or sulfuric acid or polyphosphoric acid, are esterified into the corresponding B-sulfatoalkyl or B-phosphatoalkyl groups. If the ring closure is carried out in sulfuric acid or oleum as the reaction medium, hydroxy groups which are bonded to an alkyl radical of the molecule, such as, for example, the above-mentioned β-hydroxyethyl groups of the formula radical Y 'or hydroxyalkyl groups of the formula radicals W or W ¹ and T, converted into the corresponding sulfatoalkyl groups.

At temperatures above about 35 ° C., such as at temperatures between 40 and 60 ° C., sulfo groups can also be introduced into the aromatic rings of triphendioxazine (including the corresponding aryl radicals of W, W ¹ , _T , X ¹ and _X ² ) .

Compounds of the formula (1) with Y equal to a β-sulfatoethyl group can then be converted according to known procedures into other compounds of the formula (1) according to the invention, in which Y is alkaline for the vinyl group or an ethyl group with another β-position eliminable substituents are available.

(bzw. solchen mit W¹ statt W), in welchen Y' die obengenannte Bedeutung besitzt und bevorzugt die β-Hydroxyethyl-Gruppe ist und n, R, B, W, W¹ und T die obengenannten Bedeutungen haben, wobei substituierte Alkylgruppen in diesen Resten auch hydroxysubstituierte Alkylgruppen sein können und die Gruppen -S0₂-T bevorzugt in ortho-Stellung zur Gruppe (Y'-SO₂)_n-W-B- bzw. -B-W¹-(SO₂-Y')_n gebunden sind, mit einer 1,4-Benzochinon-Verbindung der allgemeinen Formel (5)

in welcher X¹ und X² die obengenannten Bedeutungen haben und _X ³ und X⁴ zueinander gleich oder voneinander verschieden sind und jedes für ein Wasserstoffatom, eine Alkoxygruppe von 1 bis 4 C-Atomen, wie insbesondere die Methoxygruppe, oder für eine Phenoxygruppe steht oder bevorzugt ein Halogenatom, wie Fluoratom, besonders Bromatom und insbesondere Chloratom, ist, wobei X³ und X⁴ auch eine zu X und X² gleiche Bedeutung haben können, hergestellt werden.The compounds of the general formula (3) can be prepared analogously to known procedures by reacting a compound of the general formula (4)

(or those with W ¹ instead of W) in which Y 'has the abovementioned meaning and is preferably the β-hydroxyethyl group and n, R, B, W, W ¹ and T have the abovementioned meanings, substituted alkyl groups in these radicals can also be hydroxy-substituted alkyl groups and the groups -S0 ₂ -T are preferably bonded in the ortho position to the group (Y'-SO ₂ ) _n -WB- or -BW ¹ - (SO ₂ -Y ') _n , with a 1,4-benzoquinone compound of the general formula (5)

in which X ¹ and X ^{2 have} the meanings given above and _X ³ and X ⁴ are identical or different from one another and each represents a hydrogen atom, an alkoxy group of 1 to 4 carbon atoms, such as in particular the methoxy group, or a phenoxy group or preferably a halogen atom, such as fluorine atom, especially bromine atom and especially chlorine atom, where X ³ and X ^{4 can} also have the same meaning as X and X ² .

The reaction of a compound of the general formula (4) or two different amino compounds of the general formula (4), in each case in a double equivalent amount, with one equivalent of a compound of the general formula (5) to give the compound of the general formula (3) analogous to known procedures, for example in K. Venkataraman, "The Chemistry of Synthetic Dyes", Volume V, pp. 419-427 (1971), and in Ullmanns Encyklopadie der Technische Chemie, 4th ed., Volume 8, p. 240 + 241 (1974) as well as in British Patent Application Publication No. 2 019 872, in German Patent Application No. 28 23 828 and in European Patent Application Ver publication No. 0 141 996A. For example, the reaction can be carried out in an aqueous medium or in an aqueous-organic medium or in a purely organic medium, the organic solvents being polar aprotic and protic solvents, such as, for example, lower alkanols, such as methanol and ethanol, and halogenated benzenes, such as o-dichlorobenzene. However, the quinone of the formula (5) is preferably used in a more or less substantial excess, which is generally 2-20%, but can also be up to 100% or more, depending on the quinone chosen. The reaction of the amines (4) with the quinones (5) can at a temperature between 20 and 100 ^* C, preferably between 50 and 70 ° C, in the presence of an acid-binding agent, such as an alkali or alkaline earth carbonate or acetate, so for example sodium acetate, sodium carbonate or sodium bicarbonate, or an alkali or alkaline earth metal hydroxide, such as sodium hydroxide, or an oxide of an alkaline earth metal, such as magnesium oxide. If working in an aqueous or aqueous-organic medium, a pH range between 4 and 7, preferably between 5.5 and 6.5, is set.

in welcher R und T die obengenannten Bedeutungen besitzen, mit einem Amin der allgemeinen Formel (7)

in welcher B, W, Y' und n die obengenannten Bedeutungen haben, in Wasser oder einem organischen Medium, wie einem Alkanol, beispielsweise Methanol, Dioxan und Toluol, oder in einem Gemisch von Wasser und von wassermischbaren organischen Lösemitteln, unter Zusatz eines basischen, säurebindenden Mittels, wie beispielsweise Kaliumcarbonat, Magnesiumoxid, Natriumcarbonat oder Natriumhydroxid oder auch Triethylamin oder Triethanolamin, bei einer Temperatur zwischen 50 und 120'C, gegebenenfalls unter Druck, vorzugsweise zwischen 70 und 120°C. In wäßrigem Medium wird ein pH-Wert zwischen 6 und 12, bevorzugt zwischen 8 und 10, eingehalten.The aniline starting compounds of the general formula (4) are not yet known. The invention thus also relates to these compounds, processes for their preparation and their use for the synthesis of dyes. They can be prepared analogously to known procedures of the reaction of nitrochlorobenzenes prepared with amines, such as by reacting a chloronitrobenzene of the ERAL _- NEN formula (6)

in which R and T have the meanings given above, with an amine of the general formula (7)

in which B, W, Y 'and n have the meanings given above, in water or an organic medium, such as an alkanol, for example methanol, dioxane and toluene, or in a mixture of water and water-miscible organic solvents, with the addition of a basic, acid-binding agents, such as potassium carbonate, magnesium oxide, sodium carbonate or sodium hydroxide or also triethylamine or triethanolamine, at a temperature between 50 and 120'C, optionally under pressure, preferably between 70 and 120 ° C. A pH of between 6 and 12, preferably between 8 and 10, is maintained in an aqueous medium.

in welcher R, T, B, W, Y' und n die obengenannten Bedeutungen haben, können sodann nach an und für sich üblichen Methoden der Reduktion von aromatischen Nitrogruppen mittels Wasserstoff und einem metallischen Katalysator, wie einem Palladium-, Platin- oder Raney-Nickelkatalysator, unter Druck im Autoklaven oder mittels der Reduktion nach Bechamp bei Verwendung von Eisenspänen zur Verbindung entsprechend der allgemeinen Formel (4), in welcher Y' bevorzugt für die B-Hydroxy-ethyl-Gruppe steht, synthetisiert werden. Aus den B-Hydroxy-ethylsulfonyl-Verbindungen der allgemeinen Formel (4) lassen sich die entsprechenden faserreaktiven Ausgangsverbindungen (4), in denen Y' für die Vinylgruppe oder eine Ethylgruppe, die in B-Stellung einen durch Alkali eliminierbaren Substituenten enthält, steht, in allgemein bekannter Verfahrensweise der Überführung der ß-Hydroxyethylsulfonyl-Gruppe in solche Gruppen herstellen. Bevorzugt wird die ß-Hydroxy-ethylsulfonyl-Gruppe in die B-Sulfatoethylsulfonyl-Gruppe übergeführt.The nitroaniline compounds of the general formula (8) which are also obtainable in this way and which are new and according to the invention

in which R, T, B, W, Y 'and n have the meanings given above, can then be used according to conventional methods for the reduction of aromatic nitro groups by means of hydrogen and a metallic catalyst, such as a palladium, platinum or Raney Nickel catalyst, under pressure in an autoclave or by means of the Bechamp reduction using iron filings for the compound of the general formula (4), in which Y 'preferably represents the B-hydroxyethyl group, can be synthesized. The corresponding fiber-reactive starting material can be obtained from the B-hydroxyethylsulfonyl compounds of the general formula (4) Compounds (4) in which Y 'represents the vinyl group or an ethyl group which contains a substituent which can be eliminated by alkali in the B position, prepare the β-hydroxyethylsulfonyl group into such groups in a generally known manner. The β-hydroxyethylsulfonyl group is preferably converted into the B-sulfatoethylsulfonyl group.

Chloronitrobenzene compounds of the general formula (6) can be, for example, analogous to the synthesis possibilities for the production of sulfones, as for example in Houben-Weyl, Methods of Organic Chemistry, Volume IX, p. 231ff. (1955) and volume E11, p. 1132ff. (1985), so produce via the sulfinic acid derivative, as in a procedure known per se, by reducing a corresponding 1-chloro-4-nitro-benzenesulfochloride compound by means of sodium sulfite to the corresponding sulfinic acid and then oxalkylating the sulfinic acid to give β-hydroxyalkylsulfonyl Compound, which is then sulfated. The sulfato group can then be converted into the sulfo group using sodium sulfite using customary methods. For example, the 2- (ß-sulfoethylsulfonyl) -4-nitro-chlorobenzene by reacting 2- (ß-sulfatoethyl-sulfonyl) -4-nitro-chlorobenzene, which is made from 1-chloro-4-nitro by the method given above -benzenesulfochloride is available with an aqueous sodium sulfite solution at a temperature between 30 and 50 ° C and a pH between 6 and 9.5.
The carboxy-substituted alkyl sulfone compounds can also be prepared from the sulfinic acid compounds, for example by reaction with chloroacetic acid, acrylic acid or crotonic acid.

Some of the compounds of the general formula (6) can also be prepared by nitration of an appropriate alkylsulfonyl or arylsulfonylchlorobenzene compound in and of itself can be obtained in the usual way, for example analogously to the information in Example 5 of German Patent 859 462.

Starting aniline compounds of the general formula (4) are, for example, 3- (β-carboxyethylsulfonyl) -4-β (4 '- (β'-hydroxyethylsulfonyl) phenyl] ethylamino-aniline, 3- (β-sulfoethylsulfonyl) -4- β- (5 '- (β-hydroxyethylsulfonyl) benzotriazol-1'-yl] ethylamino aniline, 3- (β-sulfoethylsulfonyl) -4-γ- [5'-β-hydroxyethylsulfonyl) benzotriazole-1'- yl] -propylamino-aniline, 3- (ß-sulfo-propylsulfonyl) -4-ß- [4 '- (β'-hydroxyethylsulfonyl) -phenyl] -ethylamino-aniline, 3- (ß-sulfoethylsulfonyl) -4- [ 3'-B-hydroxy-ethylsulfonyl-4- (N-methyl-N-β-sulfoethyl) -aminophenylamino] aniline, 3- (β-sulfoethylsulfonyl) -4- [3'-β-hydroxyethylsulfonyl-4 ' -ethylamino] -phenylamino-aniline, 3- (β-sulfoethylsulfonyl) -4- [β- (β'-hydroxyethylsulfonyl) -ethylamino] -aniline, 3- (β-sulfoethylsulfonyl) -4- [γ- (β'- hydroxyethylsulfonyl) propylamino] aniline, 3- (B-sulfoethylsulfonyl) -4 - [(4'-β-hydroxyethylsulfonylphenyl) methylamino] aniline, 3- (ß-sulfoethylsulfonyl) -4- [ß- (4'-ß'-hydroxyethylsulfonylphenoxy) ethylamino] aniline, 3- (ß-sulfoethylsulfonyl) -4- [γ - (2'-amino-4'-β'-hydroxyethylsulfonylphenylamino] propylamino aniline, 3- (ß-sulfoethylsulfonyl) -4- [3 '- (ß-hydroxyethylsulfonyl) phenylamino] aniline, 3- ( B-sulfoethylsulfonyl) -4- [3 '- (B-hydroxyethylsulfonyl) -4-methylphenylamino] aniline, 3- (β-sulfoethylsulfonyl) -4- (6' - (β-hydroxyethylsulfonyl) -8 ' -sulfo-naphth-2'-yl-amino] -aniline, 3- (β-sulfoethylsulfonyl) -4- (8 '- (β-hydroxyethylsulfonyl) -6'-sulfo-naphth-2'-yl-amino] - aniline, 3- (B-sulfoethylsulfonyl) -4- [6 ', 8'-di- (β-hydroxyethylsulfonyl) naphth-2'-ylamino] aniline and especially 3- (β-sulfoethylsulfonyl) -4- [β- (4'-β'-hydroxyethylsulfonylphenyl) ethylamino] aniline, 3- (β-sulfoethylsulfonyl) -4- [3 '- (β-hydroxyethylsulfonyl) -4-methoxyphenylamino] aniline, 3 - (β-sulfoethylsulfonyl) -4- [3 '- (β-hydroxyethylsulfonyl) -4' - (β-hydroxyethylamino) phenylamino] aniline and 3- (B-sulfoethylsulfonyl) -4- [3 '- (B- hydroxyethylsulfonyl) -4 '- (β-sulfoethylamino) phenylamino] aniline.

The benzoquinones of the general formula (5) serving as starting compounds are known in the literature in large numbers. Compounds of this type are, for example, 1,4-benzoquinone, 2-methyl-1,4-benzoquinone, 2-ethyl-1,4-benzoquinone, 2-n-propyl-1,4-benzoquinone, 2-isopropyl-1,4 -benzoquinone, 2- (ß-ethoxyethyl) -1,4-benzoquinone, 2-phenyl-1,4-benzoquinone, 2- (4'-methylphenyl) -1,4-benzoquinone, 2- (4'-methoxyphenyl) -1,4-benzoquinone, 2- (3'-chlorophenyl) -1,4-benzoquinone, 2- (4'-nitrophenyl) -1,4-benzoquinone, 2,5-dimethyl-1,4-benzoquinone, 2 -Methyl-5-ethyl-1,4-benzoquinone, 2-methyl-3-chloro-1,4-benzoquinone, 2-methyl-6-chloro-1,4-benzoquinone, 2-methyl-3,5-dichloro -1,4-benzoquinone, 2-methyl-3,5,6-tribromo-1,4-benzoquinone, 2- (4'-methylphenoxy) -3,6-dibromo-1,4-benzoquinone, 2- (3rd '-Methylphenoxy) -3,6-dibromo-1,4-benzoquinone, 2-methyl-3,5,6-trichloro-1,4-benzoquinone, 2-methyl-3-chloro-5-bromo -1,4-benzoquinone, 2-methyl-3,6-dichloro-1,4-benzoquinone, 2-methyl-3,6-dichloro-5-bromo-1,4-benzoquinone, 2-phenyl-3,6 -dichloro-1,4-benzoquinone, 2- (4'-methoxyphenyl) -3,6-dichloro-1,4-benzoquinone, 2- (4'-chlorophenyl) -3,6-dichloro-1,4-benzoch inone, 2- (4'-nitrophenyl) -3,6-dichloro-1,4-benzoquinone, 2- (4'-nitrophenyl) -3,5,6-trichloro-1,4-benzoquinone, 2,5- Dimethyl-3,6-dibromo-1,4-benzoquinone, 2,5-dimethyl-3-chloro-1,4-benzoquinone, 2-methyl-5-n-propyl-6-bromo-1,4-benzoquinone, 2-methyl-5-isopropyl-3-chloro-1,4-benzoquinone, 2-methyl-5-isopropyl-6-bromo-1,4-benzoquinone, 2- (2'-chlorophenyl) -3,5,7 -tribromo-1,4-benzoquinone, 2-methyl-3-methoxy-1,4-benzoquinone, 2,3,5,6-tetramethoxy-1,4-benzoquinone, 2,3,5,6-tetraphenoxy-1 , 4-benzoquinone, 2,3,5,6-tetra- (4'-methylphenoxy) -1,4-benzoquinone, 2,3,5,6-tetra- (4'-methoxyphenoxy) -1,4-benzoquinone , 2,3,5,6-tetra- (4'-chlorophenoxy) -1,4-benzoquinone, 2,3,5,6-tetra-4- (3'-methyl-4'-chlorophenoxy) -1, 4-benzoquinone, 2-ethyl-3,6-dimethoxy-1,4-benzoquinone, 2-chloro-3,6-dimethoxy-1,4-benzoquinone, 2,3,5-trimethoxy-1,4- benzoquinone, 2,5-dimethyl-3,6-dimethoxy-1,4-benzoquinone, 2,5-dimethyl-3,6-dimethoxy-1,4-benzoquinone, 2-methyl-3,6-dimethoxy-1, 4-benzoquinone,

2-methyl-5,6-dimethoxy-1,4-benzoquinone, 2-ethyl-3,6-dimethoxy-1,4-benzoquinone, 2-chloro-3-n-propyl-5-methoxy-1, 4-benzoquinone and 2-chloro-3,5-dimethoxy-1,4-benzoquinone, 2,3,5,6-tetrafluoro-1,4-benzoquinone and preferably 2,3,5,6-tetrabromo-1,4 -benzoquinone and in particular 2,3,5,6-tetrachloro-1,4-benzoquinone.

Starting compounds of the general formula (7) given and defined above, which contain the fiber-reactive radical of the vinylsulfone series or are their B-hydroxyethylsulfonyl derivative, are likewise known in the literature or can be prepared analogously to the procedures described in the literature. Such compounds are preferably β- (4-β'-hydroxyethylsulfonylphenyl) ethylamine, 3- (B-hydroxyethylsulfonyl) -4-methoxy-aniline, 3- (B-hydroxyethylsulfonyl) -4- (B-hydroxyethylamino) aniline and 3- (β-hydroxyethylsulfonyl) -4- (β-sulfoethylamino) aniline, furthermore β- [5- (β-hydroxyethylsulfonyl) benzotriazol-1-yl] ethylamine, γ- [5-β-hydroxyethylsulfonyl) - benzotriazol-1-yl] -n-propyl-amine, the ω- [5- (β-hydroxyethylsulfonyl) -benzotriazol-1-yl) -C ₄ -C ₆ -n-alkylamines, β- [5- (β- Hydroxy-ethylsulfonyl) benzotriazol-1-yl] ethanol, the ω- [5- (β-hydroxyethylsulfonyl) benzotriazol-1-yl] -C ₃ -C ₆ -n-alkanols, β- (5- (β -Hydroxyethylsulfonyl) -benzotriazol-1-yl] -n-propylamine, 4- [5 '- (β-Hydroxyethylsulfonyl) -benzotriazol-1'-yl] -cyclohexylamine, β- {4- [5' - (B-Hydroxyethylsulfonyl ) -benzotriazol-1 '-yl] -phenylamino} -ethylamine, β- {4- [5' - (β-Hydroxyethylsulfonyl) -benzotriazol-1'-yl] -phenylamino} - ethanol, 4- [5 '- ( B-hydroxyethylsulfonyl) benzotriazol-1'-yl] phenethylamine, β- (4-β'-hydroxyethylsulfonylphenyl) ethylamine, β- (4-β ' -Hydroxyethylsulfonyl) -benzylamine, β- (2-sulfo-4-β'-hydroxyethylsulfonyl-phenyl) -ethylamine and the other amino compounds evident from the examples or their β-hydroxyethylsulfonyl derivatives.

in welcher B, W^*, Y' und n die obengenannten Bedeutungen haben, sind noch nicht beschrieben. Sie können analog bekannten Verfahrensweisen hergestellt werden, indem man eine Verbindung der allgemeinen Formel (9)

in welcher R^*, Y' und n die obengenannten Bedeutungen haben und Hal für ein Fluor- oder Bromatom steht, mit einer Verbindung der allgemeinen Formel A-B-W^*-NH₂ , in welcher A ein Wasserstoffatom oder Acylrest, wie ein Acetyl- oder Benzoylrest, ist und B und W^* die obengenannten Bedeutungen haben und B bevorzugt die Gruppe NH ist, in einem für diese Reaktanten geeigneten Lösemittel in Gegenwart eines säurebindenden Mittels bei einer Temperatur zwischen 30 und 120°C, vorzugsweise zwischen 70 und 90°C, umsetzt.Starting compounds of the general formula (7) which contain the benzotriazole radical, ie compounds of the general formula (7a)

in which B, W ^* , Y 'and n have the meanings given above have not yet been described. They can be prepared analogously to known procedures by using a compound of the general formula (9)

in which R ^* , Y 'and n have the meanings given above and Hal represents a fluorine or bromine atom, with a compound of the general formula ABW ^{* -} NH ₂ , in which A is a hydrogen atom or acyl radical, such as an acetyl or benzoyl radical, and B and W ^{* have} the meanings given above and B is preferably the group NH, in a solvent suitable for these reactants in the presence of an acid-binding agent at a temperature between 30 and 120 ° C., preferably between 70 and 90 ° C.

in welchen

• G ein Sauerstoffatom, ein Schwefelatom, eine Sulfonylgruppe oder eine Gruppe der Formel -NH- , -N(CH₃)-oder -N(COCH₃)- bedeutet,
• R für ein Wasserstoffatom oder eine Sulfogruppe steht,
• A die obengenannte Bedeutung besitzt,
• v die Zahl 2, 3 oder 4 ist,
• _G ¹ die Gruppe -NH- oder ein Sauerstoffatom ist und
• y die Zahl 2 oder 3 bedeutet.

Starting compounds corresponding to the formula AB W ^{* -} NH ₂ are, for example, 1,2-diamino-ethane, 1,3-diamino-propane, 1,4-diamino-butane, 1,5-diamino-pentane, 1,6-diamino hexane, 1,2-diamino-propane, 1,2-diamino-butane, 1,3-diamino-butane, the N-acyl, such as the N-acetyl and N-benzoyl compounds, of the l-amino 3-methylamino propane, 1,3-diamino-2-methyl propane, 1,3-diamino-2-hydroxy propane, 1,5-diamino-2-carboxypentane, 1,3-diamino-2-phenylpropane or its derivative sulfo-substituted in the benzene residue, 1,3- or 1,4-cyclohexylene diamine, bis- (4-amino- cyclohex-1-yl) methane, 1,8-di- (aminomethyl) -naphthalene, 1,4-di- (aminomethyl) -benzene, 1,3-di- (aminomethyl) -benzene, N, N'- Bis- (B-aminoethyl) -1,4-piperidine, 1,4- or 1,3-phenylenediamine, 4-aminobenzylamine, 4-aminophenethylamine and the corresponding N-monoacyl derivatives of such compounds, furthermore compounds corresponding to one general formulas (a), (β), (y) and (δ)

in which

• G is an oxygen atom, a sulfur atom, a sulfonyl group or a group of formula -NH-, -N (CH ₃₎ or -N (COCH ₃₎ - means,
• R represents a hydrogen atom or a sulfo group,
• A has the meaning given above,
• v is the number 2, 3 or 4,
• _G ^{1 is} the group -NH- or an oxygen atom and
• y represents the number 2 or 3.

Of these, 1,2-diamino-ethane, 1,3-diamino-propane, 1,4-diamino-butane and 1,2-diamino-propane are particularly preferred.

Suitable solvents for the implementation of halogen nitro Benzenes and the amino compounds are, for example, water, alkanols of 1 to 4 carbon atoms, dioxane, toluene, the xylenes, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, dimethylformamide and N-methyl-pyrrolidone. The amine itself can also be used in excess as a solvent.

in welcher A, B, R^*, W^*, Y' und n die obengenannten Bedeutungen haben, kann in üblicher Weise, beispielsweise durch Kristallisation aus dieser Reaktionsmischung bzw. durch Abdestillieren des Lösemittels oder überschüssigen Amins oder durch Ansäuern und Filtration, isoliert werden. Die anschließende Reduktion der Nitrogruppe in der Nitroverbindung (10) zur Aminogruppe erfolgt in an und für sich bekannter Weise, so durch katalytische Hydrierung mit Wasserstoff an Palladium, Platin oder Raney-Nickel bei einer Temperatur zwischen 50 und 110^*C und bei erhöhtem Druck oder durch Reduktion nach Bechamp mit Eisen in saurem Medium, beispielsweise mit Eisen in Ethanol/Eisessig, durchgeführt werden. Die Reduktion kann in einem hierfür geeigneten Lösemittel, wie Wasser, Methanol oder Ethanol oder einer Mischung derselben, erfolgen.The nitro compound of the general formula (10) obtained

in which A, B, R ^* , W ^* , Y 'and n have the meanings given above, can be isolated in a conventional manner, for example by crystallization from this reaction mixture or by distilling off the solvent or excess amine or by acidification and filtration. The subsequent reduction of the nitro group in the nitro compound (10) to the amino group is carried out in a manner known per se, for example by catalytic hydrogenation with hydrogen over palladium, platinum or Raney nickel at a temperature between 50 and 110 ^° C. and at elevated pressure or by reduction according to Bechamp with iron in an acidic medium, for example with iron in ethanol / glacial acetic acid. The reduction can take place in a suitable solvent, such as water, methanol or ethanol or a mixture thereof.

The amino compound contained in the hydrogenation batch - after prior removal of catalysts or metallic reducing agents - can be diazotized directly, without intermediate isolation, with simultaneous ring closure to form the triazole. The diazotization is carried out in a conventional manner, for example with sodium nitrite in hydrochloric acid at a temperature between -5 ° C and + 15 ° C. Any acylamino group present in the benzotriazole compound obtained can be hydrolyzed in a conventional manner, for example in an aqueous medium at a pH greater than 12 and at a temperature of 90 to 100 ° C., to the amino group and thus to the compound of the general formula (7) will.

The compounds of general formula (1) prepared according to the invention can be separated and isolated from the synthesis solutions by generally known methods, for example either by precipitation from the reaction medium by means of electrolytes, such as sodium chloride or potassium chloride, or by evaporation of the reaction solution, for example spray drying. a buffer substance can be added to this reaction solution.

The compounds of the general formula (1) according to the invention have fiber-reactive properties and valuable dye properties. They can therefore be used for dyeing (including printing) natural, regenerated or synthetic materials containing hydroxyl groups and / or carbonamide groups, for example in the form of sheets, such as paper and leather, or in bulk, of polyamide or polyurethane, but in particular of such materials in fiber form , such as cellulose fiber materials, silk, wool and synthetic polyamide and polyurethane fibers can be used. The solutions obtained in the synthesis of the compounds according to the invention, if appropriate after adding a buffer substance, if appropriate also after concentration, can be used directly as a liquid preparation for dyeing.

The compounds of the formula (1) according to the invention can, according to the application according to the invention, be applied and fixed on the substrates mentioned, in particular on the fiber materials mentioned, by the application techniques known for water-soluble, in particular fiber-reactive, dyes, for example by using the dioxazine compound applies general formula (1) in dissolved form to the substrate or introduces it into it and on it or in it, optionally by exposure to heat and / or ^y optionally by exposure of an alkaline agent. Such staining and fixing methods have been described in numerous publications.

The present invention therefore also relates to the use of the compounds of the general formula (1) according to the invention for dyeing (including printing) materials containing hydroxyl and / or carbonamide groups and processes for their use on these substrates. The materials are preferably used in the form of fiber materials, in particular in the form of textile fibers, such as yarns, packages and fabrics. Here one can proceed analogously to known methods of application and fixation of fiber-reactive dyes.

The dyeings and prints produced with compounds of the general formula (1) according to the invention are distinguished by pure, predominantly blue shades. In particular, the dyeings and prints on cellulose fiber materials have very high color strengths and also very good light fastness properties, including good wet light and perspiration light fastness properties, as well as good hypochlorite bleaching and chlorine bathing water properties, as well as excellent wet fastness properties, such as good to very good wash fastness properties at 60 to 95 ° C, too in the presence of perborates, acid and alkaline whale, over-dyeing and perspiration fastness, alkali, acid, water and seawater fastnesses, furthermore good pleating fastness, ironing fastness and rubbing fastness. They also have good fastness to wet lying and very good acid fading when storing moist, colored material which still contains acetic acid. Furthermore, the dyeings are stable against the usual synthetic resin finishes. Some of the compounds (dyes) according to the invention are in the purity of the color and in important authenticity properties comparable to fiber-reactive anthraquinone dyes.

The following examples serve to illustrate the invention. The parts are parts by weight, the percentages represent percentages by weight, unless stated otherwise. Parts by weight relate to parts by volume such as kilograms to liters.

example 1

• a) 492 parts of 3- (β-sulfoethylsulfonyl) -4- [4'-β- (β-hydroxyethylsulfonylphenyl) ethylamino] aniline are clearly dissolved in 2000 parts of water at 60 ° C. 124 parts of chloranll are introduced, and a pH of 6 to 6.5 is maintained at a reaction temperature of about 65 ° C. during the reaction with about 90 parts of sodium bicarbonate. The mixture is stirred for a further hour, the reaction product is suctioned off at about 30 ° C., washed with 400 parts of water and dried at 70 ° C. under reduced pressure.
• b) 116 parts of the product obtained under a) are introduced into 600 parts of 15% oleum at a temperature between 20 and 25 ° C. The reaction mixture is then stirred for a further three hours at this temperature; then 48 parts of sodium peroxodisulfate are introduced in such a way that the reaction temperature can be kept at 20 to 25 ° C. The mixture is stirred for a further 10 hours at this temperature, then the batch is allowed to run on ice, the precipitated compound according to the invention is filtered off, it is redissolved in about 1000 parts of water, the pH is adjusted to 5 with sodium carbonate and, if appropriate, salted after the previous one usual clarification of the solution, with sodium chloride.

(die jeweilige ß-Sulfoethylsulfonyl-Gruppe kann auch in der anderen ortho-Stellung zur (ß-Sulfatoethylsulfonyl)-phenyl- ethylamino-Gruppe gebunden sein, befindet sich jedoch mit größerer Wahrscheinlichkeit in der in der obigen Formel angegebenen Stellung).The triphendioxazine compound according to the invention can also be obtained in the form of its sodium salt by evaporation or spray drying of the combined filtrate. Written in the form of free acid, it has the putative formula

(The respective β-sulfoethylsulfonyl group can also be bonded in the other ortho position to the (β-sulfatoethylsulfonyl) phenylethylamino group, but is more likely to be in the position indicated in the above formula).

This compound according to the invention has very good fiber-reactive dye properties. It dyes the materials mentioned in the description, in particular cellulose fiber materials, such as cotton, according to the customary techniques known in the art for the application and fixing of fiber-reactive dyes in strong, pure reddish blue tones (corresponding to color index 13 of the Color Index Hue Indication Chart) with good fastness properties, such as, in particular, good light fastness of the dry or moist dyeing, such as moistened with drinking water, good alkaline perspiration light fastness, chlorine bath fastness, hypochlorite fastness, alkaline sweat fastness, wash fastness, even in the presence of perborates, wet fastness fastness and resistance to acid storage. In aqueous solution, it shows an absorption maximum at 614 nm in the visible range.

c) The aniline compound used under a) can be prepared, for example, as follows: 330 parts of 3- (β-sulfoethylsulfonyl) -4-chloro-nltrobenzene are suspended in an aqueous sodium hydroxide solution from 48 parts of sodium hydroxide and 2600 parts of water; 320 parts of 2- [4 '- (β-hydroxyethylsulfonyl) phenyl] ethylamine hydrochloride are introduced immediately with stirring and the reaction temperature is raised to 70 ° C .; during the reaction, the pH is kept at 10 by means of an aqueous sodium hydroxide solution. After the reaction has ended, the mixture is clarified hot and adjusted to a pH of 6 to 7 with dilute hydrochloric acid. Upon cooling, the 2- (β-sulfoethylsulfonyl) -4-nitro-1- [4 '- (β-hydroxyethylsulfonyl) phenylj-ethylamino-benzene crystallizes out of the aqueous medium in high purity.

• δ = 2,61 ppm (t,2H); 3,05 ppm (t,2H); 3,43 ppm (t,2H);
• 3,46 ppm (t,2H); 3,63 ppm (m,2H); 3,70 ppm (m,2H);
• 4,82 ppm (t,OH); 7,11 ppm (d,lH); 7,27 ppm (t,NH);
• 7,68 ppm (d,2H); 7,84 ppm (d,2H); 8,24 ppm (dd,lH);
• 8,36 ppm (d,lH).

It shows the following data in the 1H-NMR analysis (in D ₆ -dimethylsulfoxide with tetramethylsilane as the internal standard):

• δ = 2.61 ppm (t, 2H); 3.05 ppm (t, 2H); 3.43 ppm (t, 2H);
• 3.46 ppm (t, 2H); 3.63 ppm (m, 2H); 3.70 ppm (m, 2H);
• 4.82 ppm (t, OH); 7.11 ppm (d, 1H); 7.27 ppm (t, NH);
• 7.68 ppm (d, 2H); 7.84 ppm (d, 2H); 8.24 ppm (dd, 1H);
• 8.36 ppm (d, 1H).

This nitro compound is reduced to the aniline compound by catalytic hydrogenation by dissolving 261 parts of the nitro compound in 1000 parts of water and hydrogenating in the presence of a Pd / C catalyst in an autoclave at a temperature of up to 100 ° C. and a hydrogen pressure of 50 bar. The catalyst is then filtered off, the filtrate acidified and cooled. The aniline compound crystallizes from it in good yield and high purity.

Example 2

a) 145 parts of 3- (β-sulfo-ethylsulfonyl) -4- [3- (β-hydroxyethylsulfonyl) -4-methoxy-phenylamino] -aniline are clearly dissolved in 600 parts of water at 60 ° C. 37 parts of chloranil are introduced and it becomes a pH of 6 to 6.5 during the reaction with about 30 parts of sodium bicarbonate at a reaction temperature of about Kept at 65 ° C. The mixture is stirred for another hour, the reaction product is suctioned off at about 20 ° C, washed with 50 parts of ethanol and dried at 60 ° C under reduced pressure.

b) 117 parts of the product obtained under a) are introduced into 1000 parts of 10% oleum at a temperature between 20 and 25 ° C. The reaction mixture is then stirred for a further three hours at this temperature; then 47 parts of sodium peroxodisulfate are introduced in such a way that the reaction temperature can be kept at 20 to 25 ° C. The mixture is stirred for a further 10 hours at this temperature, the mixture is then allowed to run on ice, adjusted to a pH between 1 and 1.5 with calcium carbonate, then to a pH of 5.5 with sodium carbonate, and the precipitate is filtered off Calcium sulfate, wash it out with water and combine the filtrates.

(die jeweilige ß-Sulfoethylsulfonyl-Gruppe kann auch in der anderen ortho-Stellung zur Phenylamino-Gruppe gebunden sein, befindet sich jedoch mit größerer Wahrscheinlichkeit in der in der obigen Formel angegebenen Stellung).The triphendioxazine compound according to the invention can be obtained in the form of its sodium salt by evaporation or spray drying of the combined filtrate. Written in the form of free acid, it has the putative formula

(the respective ß-sulfoethylsulfonyl group can also be bound in the other ortho position to the phenylamino group, is more likely to be in the position shown in the above formula).

This compound according to the invention has very good fiber-reactive dye properties. It dyes the materials mentioned in the description, in particular cellulose fiber materials, such as cotton, in accordance with the methods of application and fixation of fiber-reactive dyestuffs which are customary and known in the art, in strong, pure reddish blue tones (color index 13) with good fastness properties, such as, in particular, good light fastness the dry or moist coloring, as moistened with drinking water, good alkaline fastness to perspiration, chlorine bath fastness, hypochlorite fastness, alkaline fastness to sweat, fastness to washing, also in the presence of perborates, fastness to wet lying and resistance to acid storage. In aqueous solution, it shows an absorption maximum at 583 nm in the visible range.

• 165 Teile 3-(β-Sulfoethylsulfonyl)-4-chlor-nitrobenzol und 116 Teile 3-(β-Hydroxyethylsulfonyl)-4-methoxy- anilin werden in 1000 Teilen Wasser und in Anwesenheit von 14 Teilen Magnesiumoxid 15 Stunden bei 100°C erhitzt. Der Ansatz wird nach dem Erkalten geklärt, mit konzentrierter Salzsäure angesäuert; das synthetisierte 3-(ß-Sulfoethylsulfonyl)-4-[3-(ß-hydroxyethylsulfonyl)-4-methoxy-phenylamino]-nitrobenzol wird anschließend in hoher Reinheit mittels 150 Teilen Natriumchlorid ausgesalzen und isoliert.
• ¹H-NMR-Analyse (in D₂O):
• δ = 3,15-3,42 ppm (m,2H); 3,55-4,15 ppm (m,9H); 6,88 ppm (d,lH); 7,33 ppm (d,lH); 7,68 ppm (dd,lH); 7,8 ppm (d,1H); 8,08 ppm (dd,lH); 8,55 ppm (d,lH); die Protonen der Hydroxy-, Amino- und Sulfogruppen waren nicht sichtbar.

c) The aniline compound used under a) can be prepared, for example, as follows:

• 165 parts of 3- (β-sulfoethylsulfonyl) -4-chloro-nitrobenzene and 116 parts of 3- (β-hydroxyethylsulfonyl) -4-methoxy-aniline are heated for 15 hours at 100 ° C. in 1000 parts of water and in the presence of 14 parts of magnesium oxide . The mixture is clarified after cooling, acidified with concentrated hydrochloric acid; the synthesized 3- (ß-sulfoethylsulfonyl) -4- [3- (ß-hydroxyethylsulfonyl) -4-methoxy-phenylamino] -nitrobenzene is then salted out in high purity using 150 parts of sodium chloride and isolated.
• ¹ H-NMR analysis (in D ₂ O):
• δ = 3.15-3.42 ppm (m, 2H); 3.55-4.15 ppm (m, 9H); 6.88 ppm (d, 1H); 7.33 ppm (d, 1H); 7.68 ppm (dd, 1H); 7.8 ppm (d, 1H); 8.08 ppm (dd, 1H); 8.55 ppm (d, 1H); the protons of the hydroxy, amino and sulfo groups were not visible.

This nitro compound can then be converted into the corresponding aniline compound by hydrogenation in the presence of a nickel catalyst, for example in methanol at a temperature of about 100 ° C. and a pressure of 50 bar hydrogen.

Example 3

a) 523 parts of 3- (β-sulfoethylsulfonyl) -4- [3- (β-hydroxyethylsulfonyl) -4- (β-hydroxyethylamino) phenylamino] aniline are clearly dissolved in 2000 parts of water at 65 ° C. 124 parts of chloranil are introduced, and a pH of 6 to 6.5 is maintained at a reaction temperature of about 65 ° C. during the reaction with about 80 parts of sodium bicarbonate. The mixture is stirred for a further three hours, the reaction product is filtered off after cooling, washed with 200 parts of water and dried at 70 ° C. under reduced pressure.

b) 122 parts of the product from a) are introduced into 500 parts of 20% oleum at a temperature between 20 and 25 ° C. The reaction mixture is then stirred for a further 15 hours at this temperature; then 48 parts of sodium peroxodisulfate are introduced in such a way that the reaction temperature can be kept at 20 to 25 ° C. The mixture is stirred for a further 10 hours at this temperature, the mixture is then allowed to run on ice, is adjusted to a pH between 1 and 1.5 with calcium carbonate, then to a pH of 6 with sodium carbonate, and the precipitated calcium sulfate is filtered off , it washes out with water and combines the filtrates. Calcium ions still in solution can be precipitated with oxalic acid.

(die jeweilige β-Sulfoethylsulfonyl-Gruppe kann auch in der anderen ortho-Stellung zur Phenylamino-Gruppe gebunden sein, befindet sich jedoch mit größerer Wahrscheinlichkeit in der in der obigen Formel angegebenen Stellung).The triphendioxazine compound of the invention can be obtained in the form of its sodium salt by evaporation or spray drying the combined filtrate or lytsalzen salting-out by means of electric _T, such as sodium and potassium chloride, iso be lated. Written in the form of free acid, it has the putative formula

(The respective β-sulfoethylsulfonyl group can also be bound in the other ortho position to the phenylamino group, but is more likely to be in the position indicated in the above formula).

This compound according to the invention has very good fiber-reactive dye properties. It dyes the materials mentioned in the description, in particular cellulose fiber materials, such as cotton, according to the methods of application and fixation of fiber-reactive dyes in strong, pure greenish blue tones (color code 14) with good fastness properties, particularly good Lightfastness of dry or moist dyeing, as if moistened with drinking water, good alkaline perspiration light fastness, chlorine bath fastness, hypochlorite fastness, alkaline sweat fastness, washfastness, even in the presence of perborates, wet fastness and acid storage stability. In aqueous solution, it shows an absorption maximum at 620 nm in the visible range.

c) The aniline compound used under a) can be prepared analogously to Example 2c), 131 parts of 3- (β-hydroxyethylsulfonyl) -4- (β-hydroxyethylamino) aniline being used as the aniline compound. After the reaction has been carried out and the mixture has been clarified at a pH of 6, the hydrogenation takes place directly in the solution.

Examples 4 to 30

In the following table examples, further triphendioxazine compounds according to the general formula (1) according to the invention are described with the aid of their formula residues (where W is identical to W and R represents a hydrogen atom). They can be prepared in the manner according to the invention, for example analogously to the above exemplary embodiments by reacting a 1,4-benzoquinone compound corresponding to the general formula (5) which can be seen from the respective table example with a compound of the general formula (4) in which R represents a Is hydrogen atom and B, W, T and n have the meanings evident from the respective table example, with the B-hydroxyethyl group for the formula radical Y 'instead of the β-sulfatoethyl group for compound Y in the table (4) stands, and by subsequent sulfation and cyclization. These triphendioxazine compounds according to the invention likewise have very good fiber-reactive dye properties and, on the materials mentioned in the description, such as in particular cellulose fiber materials, provide strong, true dyeings with the shade indicated on cotton in the respective table example (with the color index given in brackets according to the Color Index Hue Indication chart).

Example 31

werden in 2000 Teilen Wasser bei pH 6 und 60'C gelöst. 124 Teile Chloranil werden eingetragen, und es wird während der Reaktion mit etwa 90 Teilen Natriumbicarbonat ein pH-Wert von 6 bis 6,5 bei einer Reaktionstemperatur von etwa 65'C gehalten. Der Ansatz wird noch 4 Stunden nachgerührt, das Reaktionsprodukt bei etwa 30°C abgesaugt, mit 1000 Teilen Wasser gewaschen und unter reduziertem Druck bei 70°C getrocknet.a) 547 parts of the compound of the formula

are dissolved in 2000 parts of water at pH 6 and 60'C. 124 parts of chloranil are introduced, and a pH of 6 to 6.5 is maintained at a reaction temperature of about 65'C during the reaction with about 90 parts of sodium bicarbonate. The mixture is stirred for a further 4 hours, the reaction product is suctioned off at about 30 ° C., washed with 1000 parts of water and dried at 70 ° C. under reduced pressure.

b) 127 parts of the product obtained under a) are introduced into 650 parts of 13% oleum at a temperature between 20 and 25 ° C. The reaction mixture is then stirred for a further about 12 hours at this temperature, then 48 parts of sodium peroxodisulfate are introduced in such a way that the reaction temperature can be kept at 20 to 25 ° C. The mixture is stirred for a further 10 hours at this temperature, then the batch is allowed to run on ice, the precipitated compound according to the invention is filtered off, it is redissolved in about 1000 parts of water, the pH is adjusted to 5 with sodium carbonate and the mixture is salted, if appropriate previous usual clarification of the solution with sodium chloride.

(die jeweilige B-Sulfoethylsulfonyl-Gruppe kann auch in der anderen o-Stellung zur (ß-Sulfatoethylsulfonyl)-benztria- zolyl-propylamino-Gruppe gebunden sein, befindet sich jedoch mit größerer Wahrscheinlichkeit in der in der obigen Formel angegebenen Stellung).The triphendioxazine compound according to the invention can also be obtained in the form of its sodium salt by evaporation or spray drying of the combined filtrate. Written in the form of free acid, it has the putative formula

(The respective B-sulfoethylsulfonyl group can also be bonded in the other o-position to the (β-sulfatoethylsulfonyl) -benztriazolyl-propylamino group, but is more likely to be in the position indicated in the above formula).

This compound according to the invention has very good fiber-reactive dye properties. It dyes the materials mentioned in the description, in particular cellulose fiber materials, such as cotton, according to the procedures known in the art for the application and fixation of fiber-reactive dyes in strong, pure reddish blue tones (corresponding to color index 13 of the Col.Index Hue Indication Chart ) with good fastness properties, such as, in particular, good light fastness of the dry or moist dyeing, such as moistened with drinking water, good alkaline perspiration fastness, chlorine bath fastness, hypochlorite fastness, alkaline sweat fastness, wash fastness, even in the presence of perborates, wet fastness fastness and resistance to acid storage. In aqueous solution, it shows an absorption maximum at 617 nm in the visible range.

in hoher Ausbeute und Reinheit aus.c) The aniline compound used in a) can be prepared as follows, for example: 352 parts of the sodium salt of 2- (B-sulfoethylsulfonyl) -4-nitro-chlorobenzene are added to a 40 ^* C vorgeheiz mixture of 270 parts of y- [5- (B-hydroxyethylsulfonyl) benzotriazol-1-yl] n-propylamine in 1000 parts of water and 550 parts of triethanolamine. The mixture is heated to 100 to 110 ° C. in the course of 3 hours, the water being partially distilled off. The mixture is stirred for a further 5 hours at 115 to 120 ° C. for quantitative conversion, 2000 parts of water are added at 100 ° C. and the solution is clarified at 80 to 90 ° C. The sodium salt of the compound of the formula crystallizes from the aqueous medium on cooling and after the addition of NaCl

in high yield and purity.

• 6 = 2,3 ppm (m,2H); 2,7 ppm (m,2H); 3,5 ppm (m,2H); 3,6 ppm (m,4H): 3,7 ppm (m,2H): 4,9 ppm (t,2H): 4,95 ppm (t,OH), 7,1 ppm (d,lH); 7,37 ppm (t,NH): 8,03 ppm (dd,lH); 8,22 ppm (d,lH); 8,25 ppm (dd,lH); 8, 38 ppm ( d,1H) ; 8, 62 ppm (s,1H) .

It shows the following data in the 1H NMR analysis (in D ₆ - DMSO with TMS as the internal standard):

• 6 = 2.3 ppm (m, 2H); 2.7 ppm (m, 2H); 3.5 ppm (m, 2H); 3.6 ppm (m, 4H): 3.7 ppm (m, 2H): 4.9 ppm (t, 2H): 4.95 ppm (t, OH), 7.1 ppm (d, lH); 7.37 ppm (t, NH): 8.03 ppm (dd, lH); 8.22 ppm (d, 1H); 8.25 ppm (dd, 1H); 8.38 ppm (d, 1H); 8, 62 ppm (s, 1H).

This nitro compound is reduced to the aniline compound by catalytic hydrogenation, by dissolving 289 parts of the nitro compound in 1000 parts of water and hydrogenating it in the presence of a Pd / C catalyst in an autoclave at a temperature of up to 100 ° C. and a hydrogen pressure of 50 bar. The catalyst is then filtered off.

The hydrogenation product can be used directly for the reaction according to a).

• 260 Teile γ-(4-(B-Hydroxyethylsulfonyl)-2-amino-phenylamino)]-n-propylamin werden in etwa 1800 Teilen einer salzsauren wäßrigen Lösung bei 0 bis 5°C mittels einer wäßrigen Natriumnitritlösung in üblicher Weise diazotiert. Der Ringschluß erfolgt sofort und quantitativ.

d) The 5- (ß-hydroxyethylsulfonyl) benzotriazolyl propylamino compound used under c) can be prepared, for example, as follows:

• 260 parts of γ- (4- (B-hydroxyethylsulfonyl) -2-aminophenylamino)] - n-propylamine are diazotized in about 1800 parts of an aqueous hydrochloric acid solution at 0 to 5 ° C. using an aqueous sodium nitrite solution in the customary manner. The ring closure takes place immediately and quantitatively.

• δ = 2,24 ppm (m,2H); 2,85 ppm (m,2H); 3,6 ppm (m,4H); 4,92 ppm (t,2H); 8,04 ppm (dd,1H); 8,27 ppm (d,1H); 8,6 ppm (s,1H); mobile Protonen (OH, NH₂)

The solution can be used directly in c). An isolated sample shows the following data in the 1H-NMR analysis (in D ₆ -DMSO with TMS as internal standard):

• δ = 2.24 ppm (m, 2H); 2.85 ppm (m, 2H); 3.6 ppm (m, 4H); 4.92 ppm (t, 2H); 8.04 ppm (dd, 1H); 8.27 ppm (d, 1H); 8.6 ppm (s, 1H); mobile protons (OH, NH ₂ )

• 530 Teile 4-(ß-Hydroxyethylsulfonyl)-2-nitro-chlorbenzol werden bei 70 bis 80°C langsam in 750 Teile n-Propylendiamin eingetragen. Nach quantitativer Umsetzung wird der Ansatz erforderlichenfalls auf Wasser ausgerührt und das Produkt abgesaugt. Man erhält die Nitroverbindung in guter Ausbeute und hoher Reinheit mit einem Fp. von 110 bis 112°C. Sie zeigt folgende Daten in der 1H-NMR-Analyse (im D₆-DMSO mit TMS als inneren Standard):
• δ = 1,7 ppm (m,2H); 2,66 ppm (t,2H); 3,5 ppm (m,4H); 3,68 ppm (m,2H); 7,25 ppm (d,1H); 7,9 ppm (dd,1H); 8,5 ppm (d,1H); mobile Protonen (NH₂, OH).

e) The 4- (B-hydroxyethylsulfonyl) -2-aminophenylaminopropylamine compound used under d) can be obtained, for example, as follows:

• 530 parts of 4- (ß-hydroxyethylsulfonyl) -2-nitro-chlorobenzene are slowly added to 750 parts of n-propylenediamine at 70 to 80 ° C. After quantitative implementation, the batch is stirred on water if necessary and the product is suctioned off. The nitro compound is obtained in good yield and high purity with an mp of 110 to 112 ° C. It shows the following data in the 1H-NMR analysis (in D ₆ -DMSO with TMS as the internal standard):
• δ = 1.7 ppm (m, 2H); 2.66 ppm (t, 2H); 3.5 ppm (m, 4H); 3.68 ppm (m, 2H); 7.25 ppm (d, 1H); 7.9 ppm (dd, 1H); 8.5 ppm (d, 1H); mobile protons (NH ₂ , OH).

This nitro compound is reduced to the aniline compound by catalytic hydrogenation by hydrogenating 303 parts of the nitro compound in 1200 parts of water in the presence of a Pd / C catalyst in an autoclave at a temperature of up to 100 ° C. and a hydrogen pressure of 50 bar. The catalyst is then filtered off; the filtrate can be processed directly in d).

• δ = 1,9 ppm (m, 2H) ; 2,88 ppm (t,2H); 3, 2 ppm (m, 4H ) ; 3,58 ppm (m,2H); 6,51 ppm ( dd,1H ) ; 6,92 ppm (d,lH); 6,96 ppm (dd,lH); mobile Protonen bei 4,9 ppm (OH), 5,2 ppm (NH₂ ) , 5,74 ppm (NH) und 8,2 ppm (NH2).

An isolated sample shows the following data in the 1H-NMR analysis (in D ₆ -DMSO with TMS as internal standard):

• δ = 1.9 ppm (m, 2H); 2.88 ppm (t, 2H); 3.2 ppm (m, 4H); 3.58 ppm (m, 2H); 6.51 ppm (dd, 1H); 6.92 ppm (d, 1H); 6.96 ppm (dd, 1H); mobile protons at 4.9 ppm (OH), 5.2 ppm (NH ₂ ), 5.74 ppm (NH) and 8.2 ppm (NH2).

• 260 Teile 2-(ß-Hydroxyethylsulfonyl)-4-nitro-chlorbenzol werden in 800 Teilen 100 %iger Schwefelsäure und 400 Teilen 20%igem Oleum quantitativ in den Schwefelsäureester überführt, der sodann durch Ausrühren auf Eis/Kochsalz ausgefällt, unverzüglich abgesaugt und mit 20%iger wäßriger NaCl-Lösung säurefrei gewaschen (Ausbeute nahezu quantitativ) und anschließend in 1500 Teilen Wasser bei 50°C gelöst wird. Eine Lösung von 125 Teilen Na₂SO₃ in 400 Teilen Wasser wird schnell zugegeben. Nach kurzer Mischungszeit erfolgt spontan eine Fällung. Nach 1-stündigem Nachrühren bei 50°C fällt der pH auf ca. 4. Man saugt unterhalb 10°C ab und trocknet das Produkt gegebenenfalls bei 80°C unter reduziertem Druck.
• Es zeigt folgende Daten in der 1H-NMR Analyse (in D₆-DMSO mit TMS als inneren Standard):
• 6 = 2,7 ppm (m,2H); 3,8 ppm (m,2H); 8,06 ppm (dd,lH); 8,55 ppm (dd,lH); 8,64 ppm (d,lH).

f) The chloronitro compound used under c) can be obtained, for example, as follows:

• 260 parts of 2- (ß-hydroxyethylsulfonyl) -4-nitro-chlorobenzene are transferred quantitatively into 800 parts of 100% sulfuric acid and 400 parts of 20% oleum in the sulfuric acid ester, which is then precipitated by stirring on ice / sodium chloride, immediately suctioned off and with 20% aqueous NaCl solution washed acid-free (yield almost quantitative) and then dissolved in 1500 parts of water at 50 ° C. A solution of 125 parts Na ₂ SO ₃ in 400 parts water is added quickly. After a short mixing time, precipitation occurs spontaneously. After stirring for 1 hour at 50 ° C, the pH drops to about 4. It is suctioned off below 10 ° C and the product is dried, if necessary, at 80 ° C under reduced pressure.
• It shows the following data in the 1H-NMR analysis (in D ₆ -DMSO with TMS as internal standard):
• 6 = 2.7 ppm (m, 2H); 3.8 ppm (m, 2H); 8.06 ppm (dd, 1H); 8.55 ppm (dd, 1H); 8.64 ppm (d, 1H).

Examples 32 to 70

(worin M die in der Beschreibung angegebene Bedeutung hat) mit Hilfe ihrer Formelreste beschrieben (hierin stellt der Rest W^x jeweils die "spiegelbildliche" Gruppe des aufgezeigten Restes W^* dar). Sie lassen sich in erfindungsgemäßer Weise, beispielsweise analog den obigen Ausführungsbeispielen durch Umsetzung einer aus dem jeweiligen Tabellenbeispiel ersichtlichen 1,4-Benzochinon-Verbindung entsprechend der allgemeinen Formel (5) mit einer Verbindung der allgemeinen Formel (4A)

und nachträglicher Sulfatierung und Cyclisierung, herstellen. Diese erfindungsgemäßen Triphendioxazin-Verbindungen besitzen ebenfalls sehr gute faserreaktive Farbstoffeigenschaften und liefern auf den in der Beschreibung genannten Materialien, wie insbesondere Cellulosefasermaterialien, farbstarke, echte Färbungen mit dem in dem jeweiligen Tabellenbeispiel auf Baumwolle angegebenen Farbton (mit der in Klammern angegebenen Farbkennzahl nach Colour Index Hue Indication Chart).

The following table examples show further triphendioxazine compounds according to the invention corresponding to a general formula (IA)

(where M has the meaning given in the description) with the aid of its formula residues (here the residue W ^x represents the "mirror image" group of the indicated residue W ^* ). They can be prepared in the manner according to the invention, for example analogously to the above exemplary embodiments, by reacting a 1,4-benzoquinone compound corresponding to the general formula (5) shown in the respective table example with a compound of the general formula (4A)

and subsequent sulfation and cyclization. These triphendioxazine compounds according to the invention likewise have very good fiber-reactive dye properties and, on the materials mentioned in the description, such as in particular cellulose fiber materials, provide strong, true dyeings with the shade indicated on cotton in the respective table example (with the color index given in brackets according to the Color Index Hue Indication chart).

Claims (21)

1. Water-soluble triphendioxazine compound according to the general formula (1)

in which mean: T is an optionally substituted alkyl group of 1 to 6 carbon atoms, with the exception of a radical of the group Y defined below, where the alkyl group is also formed by hetero groups consisting of groups of the formulas -0-, -S-, -NH- and -N ( R ') - are selected with R' of the meaning given below, can be interrupted, or is an optionally substituted aryl group; B is an oxygen or sulfur atom or an amino group of the formula -NH- or -N (R ') -, in which R 'is an alkyl group of 1 to 6 carbon atoms, which may be substituted; W is a bivalent, optionally substituted aliphatic, optionally substituted by alkyl (C ₅ -C ₁₀ ) -cycloaliphatic, optionally substituted by alkyl aliphatic- (C ₅ -C ₈ ) -cycloaliphatic, optionally substituted araliphatic or optionally substituted aromatic-carbocyclic radical or a benzotriazole residue combined with one of these residues, it being possible for the aliphatic residues in W to be interrupted by hetero groups which consist of the groups -O-, -S-, -SO ₂ -, -CO-, 1,4-piperidino, - _NH - and -N (R ^o ) -, wherein R ^{O has} one of the meanings of R ' or is an alkanoyl group of 2 to 5 carbon atoms, are selected and / or aliphatic and aryl radicals can be connected to one another by such a hetero group; W ^l has a meaning given for W and is the same as or different from W; R is a hydrogen atom or an alkyl of 1 to 6 C atoms, an alkoxy of 1 to 5 C atoms, a halogen, carboxy or sulfo; _X ¹ is a hydrogen atom or a halogen atom, a cycloalkyl group of 5 to 8 C atoms, an aralkyloxy group, an alkoxy group of 1 to 4 C atoms, an aryloxy group, an alkyl group of 1 to 4 C atoms, an aryl group, an aralkyl group , a cyano group, a carboxy group, a carbalkoxy group of 2 to 5 carbon atoms, an arylamino group, a carbamoyl group, an N-alkyl-carbamoyl group or N, N-dialkyl-carbamoyl group with alkyl radicals of 1 to 4 carbon atoms each Atoms, an N-aryl-carbamoyl group, an alkanoylamino group of 2 to 5 carbon atoms or an aroylamino group, the aryl radicals in these substituents mentioned being preferably phenyl radicals which are also substituted by 1 or 2 substituents from the group halogen, nitro, alkyl from 1 to 4 carbon atoms, alkoxy from 1 to 4 carbon atoms, carboxy and sulfo; X ² is identical to or different from X ¹ and has one of the meanings given for X; the group -S0 ₂ -T is preferably bound in the ortho position to the group -BW- (S0 ₂ -Y) _n or -BW ^l - (SO ₂ -Y) _n ; n is the number 1 or 2; Y is the vinyl group or an ethyl group which contains a substituent which can be eliminated by an alkali in the β position; Of the sulfo and sulfato groups which can be contained in the molecule (1), the molecule (1) contains at least one, preferably at least two, of them. 2. Compound according to claim 1, characterized in that R is a hydrogen atom. 3. A compound according to claim 1 or 2, characterized in that B is an amino group -NH-. 4. Compound according to claim 1, 2 or 3, characterized in that W or W is a β- (p-phenylene) ethylene group or a 4-methoxy-1,3-phenylene or a 4- (β-sulfatoethylamino) Is 1,3-phenylene or a 4- (β-sulfoethylamino) -1,3-phenylene group. 5. A compound according to claim 1, 2 or 3, characterized in that W is a divalent radical of the general formula (2B)

and _W ^{1 is} a divalent radical of the general formula (2 _A )

is in which the two R ^* , the same or different from each other, each represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a halogen atom, a carboxy group or a sulfo group and W ^x and W ^* , identical to or different from one another, each a bivalent, optionally substituted aliphatic, optionally substituted by alkyl (C ₅ -C ₁₀ ) cycloaliphatic, optionally substituted by alkyl tuiert aliphatic- (C _S -C ₈ ) -cycloaliphatic, optionally substituted araliphatic or optionally substituted aromatic-carbocyclic radical, where the aliphatic radicals in W ^* or W ^x can be interrupted by hetero groups which are selected from the groups of the formulas -O -, -S-, -SO ₂ -, -CO-, 1,4-piperidino, -NH- and -N (R °) -, in which R ° is an alkyl group of 1 to 6 carbon atoms, which is substituted may be, or is an alkanoyl group of 2 to 5 carbon atoms, are selected, and / or wherein aliphatic and aryl radicals can be connected to one another by such a hetero group. 6. A compound according to claim 5, characterized in that W ^* and W ^x both mean the 1,2-ethylene or 1,3-propylene radical. 7. A compound according to any one of claims 1 to 6, characterized in that T is a β-sulfoethyl group. 8. A compound according to any one of claims 1 to 6, characterized in that T is an alkyl group of 2 or 3 carbon atoms which is substituted by a sulfo or carboxy group. 9. A compound according to any one of claims 1 to 8, characterized in that X ¹ and X ² both represent a chlorine or a bromine atom. 10. A compound according to any one of claims 1 to 8, characterized in that X ¹ and X ² both represent a chlorine atom. 11. A compound according to any one of claims 1 to 10, characterized in that Y is the β-sulfatoethyl group. 12. A compound according to claim 1 according to the general form (la)

in which X represents a bromine atom or preferably a chlorine atom, M is a hydrogen atom or preferably an alkali metal atom, such as in particular sodium, p represents the number 2 or 3, preferably 2, R "is a sulfo, sulfato _- or carboxy, preferably sulfo, in the case of p = 2, however, does not mean a sulfato group, and W represents a phenylene radical, preferably meta-phenylene radical, which can be substituted by methyl, ethyl, chlorine, methoxy or ethoxy, or a group of the formula (2a), (2b) or (2c)

with M has the meaning given above, where in the formulas (2b) and (2c) the phenylene radical is preferably a meta-phenylene radical and the amino group is preferably bonded para to the other amino group corresponding to the formula radical B, and W means such a residue, indicated for W, but arranged "mirror image". 13. A process for the preparation of the compounds mentioned and defined in claim 1, characterized in that a compound of the general formula (3)

(in which Y 'is the vinyl group, the β-hydroxyethyl group or an ethyl group which, in the β position, contains a substituent which can be eliminated by an alkali, and n, R, B, _W , W ¹ , T, X ¹ and X ² have the meanings given in claim 1, where substituted alkyl groups in these radicals can also be hydroxy-substituted alkyl groups and the groups -S0 ₂ -T preferably in the ortho position to the group -BW- (SO ₂ -Y ') _n or -BW ¹ - (SO ₂ -Y ') _{n are} bonded) in an acidic medium and preferably in the presence of an oxidizing agent to triphendioxazine, where appropriate before or simultaneously with the cyclization or only after the cyclization reaction, optionally present hydroxyalkyl groups by means of a sulfating or phosphating agent for the corresponding β-sulfato-alkyl or ß-phosphatoalkyl groups are esterified and, if appropriate, sulfo groups are simultaneously introduced into aryl radicals. 14. The method according to claim 13, characterized in that one carries out the ring closure in the presence of peroxodisulfate. 15. Use of the compounds of the general formula (1) mentioned and defined in claim 1 or the compounds of the general formula (1) prepared according to claim 13 for dyeing (including printing) material containing hydroxyl and / or carbonamide groups, in particular fiber material. 16. A process for dyeing (including printing) material containing hydroxyl and / or carbonamide groups, in particular fiber material, in which a dye is applied to or introduced into the material and fixed by means of heat and / or by means of an acid-binding agent, characterized that a dye of a compound of the general formula (1) mentioned and defined in claim 1 is used. 17. Compound of the general formula (4)

in which Y 'is the vinyl group, the β-hydroxyethyl group or an ethyl group which contains a substituent which can be eliminated by an alkali in the B position, and R, T, B, W and n have the meanings given in Claim 1 and the group -S0 ₂ -T is preferably bound in the ortho position to the group -BW- (S0 ₂ -Y ') _n . 18. Compound of the general formula (8)

in which Y 'is the vinyl group, the B-hydroxyethyl group or an ethyl group which contains a substituent which can be eliminated by an alkali in the β-position, and R, T, B, W and n have the meanings given in Claim 1 and the group -S0 ₂ -T is preferably bound in the ortho position to the group -BW- (SO ₂ -Y ') _n . 19. A compound according to claim 17 or 18, characterized in that W is a divalent radical of the general formula (2B)

and W ^{l is} a divalent radical of the general formula (2A)

is in which the two R ^* , the same or different from each other, each represents a hydrogen atom, an alkyl group of 1 to 4 carbon atoms, an alkoxy group of 1 to 4 carbon atoms, a halogen atom, a carboxy group or a sulfo group and W ^x and W ^* , identical to or different from one another, each a bivalent, optionally substituted aliphatic, optionally substituted by alkyl (C ₅ -C ₁₀ ) cycloaliphatic, optionally substituted by alkyl aliphatic (C ₅ -C ₈ ) cycloaliphatic, optionally substituted araliphatic or optionally substituted aromatic-carbocyclic radical, the aliphatic radicals in W ^* or W ^X can be interrupted by hetero groups which consist of the groups of the formulas -0-, -S-, -SO ₂ -, -CO-, 1,4-piperidino, -NH- and -N (R °) -, in which R ^{0 is} an alkyl group of 1 to 6 C atoms, which may be substituted, or an alkanoyl group of 2 to 5 C atoms, are selected, and / or where aliphatic and aryl radicals may be linked to one another by such a hetero group. 20. A process for the preparation of a compound of the general formula (4) specified and defined in claim 17 or a compound of the general formula (8) specified and defined in claim 18, characterized in that a compound of the general formula (6)

in which R and T have the meanings given in claim 17, with an amino compound of the general formula (7)

in which B, W, Y 'and n have the meanings given in claim 17, with the addition of a basic acid-binding agent at a temperature between 20 and 120 ° C and optionally in the nitro compound of the general formula (8) thus obtained the nitro group reduced to the amino group. 2 ₁ . Use of the compound of the general formula (4) of claim 17 or the compound of the general formula (8) of claim 18 for the synthesis of dyes, in particular triphendioxazine compounds of the general formula (1) according to claim 1.